CN105849601A - Polarizer, and polarizing plate and polarizing laminate film provided with same - Google Patents

Polarizer, and polarizing plate and polarizing laminate film provided with same Download PDF

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Publication number
CN105849601A
CN105849601A CN201480071287.5A CN201480071287A CN105849601A CN 105849601 A CN105849601 A CN 105849601A CN 201480071287 A CN201480071287 A CN 201480071287A CN 105849601 A CN105849601 A CN 105849601A
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China
Prior art keywords
film
polariser
resin
base material
polarization plates
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Granted
Application number
CN201480071287.5A
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Chinese (zh)
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CN105849601B (en
Inventor
九内雄朗
九内雄一朗
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3075—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state for use in the UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)

Abstract

Provided is a polarizer that has a maximum absorbance of 0.70 or less at a wavelength of 280-320 nm. Also provided is a polarizing plate that comprises the polarizer and a protective film that is stacked on the polarizer via an adhesive layer that comprises a cured product of a translucent adhesive. Also provided is a polarizing laminate film that comprises a substrate film and the polarizer, said polarizer being provided to both surfaces of the substrate film.

Description

Polariser and there is polarization plates and the polarizability stacked film of this polariser
Technical field
The present invention relates to polariser and there is polarization plates and the polarizability stacked film of this polariser.
Background technology
Polarization plates is widely used in the display devices such as liquid crystal indicator, the most extensively uses In various mobile devices such as smart mobile phone, flat board PC.It is said that in general, polarization plates has use glue Protecting film is fitted in the composition of the one or two sides of polariser by stick.
At patent documentation 1～8 (Japanese Unexamined Patent Publication 2013-228726 publication, Japanese Unexamined Patent Publication 2013-210513 publication, Japanese Unexamined Patent Publication 2012-144690 publication, Japanese Unexamined Patent Publication 2009-109994 publication, Japanese Unexamined Patent Publication 2009-139585 publication, Japanese Unexamined Patent Publication 2010-091603 publication, Japanese Unexamined Patent Publication 2010-091602 publication, Japanese Unexamined Patent Publication 2008-170717 publication) in, describe use photo-curable adhesive and protecting film is fitted in The polarization plates of polariser.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2013-228726 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2013-210513 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-144690 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2009-109994 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2009-139585 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2010-091603 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2010-091602 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2008-170717 publication
Summary of the invention
Invent problem to be solved
In recent years, as the protecting film of polariser, the cyclenes hydro carbons that moisture permeability is relatively low is gradually used Resin, olefine kind resin, acrylic resin, polyethylene terephthalate resinoid etc. Material replaces utilizing aqueous adhesive to carry out the moisture permeability fitted as cellulosic resin Higher material.But, even if the low material of such moisture permeability uses aqueous adhesive the most not Fully can adhere to polariser, thus use in many cases photo-curable adhesive etc. with partially The device that shakes is gluing.
When using photo-curable adhesive, it is possible to the cured layer of this adhesive goes bad because of light, The most such as it is expected in protecting film, containing UV absorbent, make display dress to be able to ensure that Light resistance when putting.Application type phase retardation film is such as formed on the surface of protecting film it addition, also have Such situation.In these cases, the ultraviolet ray transmissivity of protecting film side significantly reduces, When irradiating light from protecting film side, there is the undesirable condition that adhesive can not be made fully to solidify.
As the method solving this undesirable condition, can enumerate: the use as known technology exists The light in the wave-length coverage of the about 370nm～about 420nm of visible ray with absorption band gathers Close initiator or the photosensitizer method etc. as the composition of photo-curable adhesive.But, for For the method, owing to the range expansion of Photoepolymerizationinitiater initiater or the absorbing wavelength of photosensitizer extremely can See light region, thus polarization plates itself colours, it is possible to produce polarization plates can not be kept The undesirable condition of neutral (not colored) tone.Even if it addition, obtaining neutralc tint in the early stage Polarization plates, after making display device, makes the reaction of unreacted initiator due to exterior light Gradually carry out, it is possible to produce the undesirable condition that tone changes compared with design load.
In view of the above problems, it is an object of the invention to provide a kind of irradiation that can pass through light will Photo-curable adhesive fully solidifies and keeps the polariser of neutralc tint, and has this polarization The polarization plates of device and polarizability stacked film.
Means for solving the above
[1] a kind of polariser, the maximum absorbance under its wavelength 280nm～320nm is 0.70 Below.
[2] a kind of polarization plates, it has: the polariser described in above-mentioned [1], and across comprising light The adhesive layer of the solidfied material of permeability adhesive is layered in the protecting film on described polariser.
[3] polarization plates described in above-mentioned [2], wherein, under the wavelength 365nm of described protecting film Light transmittance is less than 5%.
[4] above-mentioned [2] or [3] described in polarization plates, wherein, described photo-curable adhesive contains Maximum absorption wavelength Photoepolymerizationinitiater initiater between 280nm～320nm.
[5] above-mentioned [2]～[4] according to any one of polarization plates, wherein, the thickness of described polariser Degree is below 10 μm.
[6] a kind of polarizability stacked film, it has: base material film, and is arranged on the two of this base material film The polariser described in above-mentioned [1] in face.
Invention effect
Can be by the irradiation of light by abundant for photo-curable adhesive in accordance with the invention it is possible to provide Solidification and the polariser of holding neutralc tint, and there is polarization plates and the polarizability of this polariser Stacked film.
Accompanying drawing explanation
Fig. 1 is the cross-sectional schematic of an example of the layer composition of the polarization plates representing the present invention.
Fig. 2 is to represent the state when polarization plates shown in Fig. 1 being arranged on display unit Cross-sectional schematic.
Fig. 3 is the flow chart of a preference of the manufacture method of the polarization plates representing the present invention.
Fig. 4 is an example of the layer composition of the stacked film that expression is obtained by resin bed formation process Cross-sectional schematic.
Fig. 5 is that the section view of an example of the layer composition of the stretched film that expression is obtained by stretching process is shown It is intended to.
Fig. 6 is an example of the layer composition of the polarizability stacked film that expression is obtained by dyeing process Cross-sectional schematic.
Fig. 7 is that the section view of an example of the layer composition of the laminating film that expression is obtained by bonding process is shown It is intended to.
Detailed description of the invention
<polarization plates>
Fig. 1 is the cross-sectional schematic of an example of the layer composition of the polarization plates representing the present invention.Such as figure Shown in 1 polarization plates 1 represented, the polarization plates of the present invention can be to have polariser 5 and across glue Adhesive layer 15 is layered in the protected film of one-side band of the protecting film 10 on a face of polariser 5 Polarization plates.Fig. 2 is to represent when the polarization plates shown in Fig. 1 being arranged on display unit The cross-sectional schematic of state.As in figure 2 it is shown, protecting film 10 is for be arranged in display by polarization plates 1 Be arranged in time on unit 4 outside protecting film, polarization plates 1 is arranged in display unit 4 Time upper, typically formed the protecting film of outmost surface.Polarization plates 1 can use and be arranged on partially The adhesive phase 2 of outer surface of device 5 of shaking configures, fits on display unit 4.
(1) polariser
In the present invention, the maximum absorbance under wavelength 280nm～320nm of polariser is 0.7 Hereinafter, more preferably less than 0.68.
Herein, absorbance is the value that can measure with absorptiometer etc., measures as incident illumination Natural light (light of wavelength 280nm～320nm) is incident to transmission during sample (polariser) Light intensity, and obtained by following formula.
Absorbance=-log10(T/T0)
Herein, T0Be incident intensity, T be transmitted intensity.
It should be noted that the measurement result of the absorbance of polariser is according to the polarization shape of incident illumination State and change.Such as, different according to absorptiometer, owing to being present in light source to sample (polariser) Between mirror or the impact of optical element etc. and somewhat polarize or comprise the polarizations such as prism Light resolution element, therefore should be noted that when measuring.In the case of such determinator, After a certain goniometry polariser, again it is measured same polarization in the orientation of 90-degree rotation Device, by the mean value calculation absorbance of these transmitted intensities, such that it is able to get rid of incident illumination The impact of polarization direction.
By using such polariser, across photo-curable adhesive, protecting film is being layered in Under state on polariser, during from polariser side towards adhesive irradiation ultraviolet radiation (UV-B etc.), Ultraviolet readily penetrates through polariser, therefore can form the glue that photo-curable adhesive fully solidifies Adhesive layer.
It addition, when protecting film and polariser gluing, even if from polariser side incident illumination, also Can effectively carry out the solidification of photo-curable adhesive, though the kind of therefore protecting film, all Can stably manufacture polarization plates.This effect is especially to have when making the polariser of below 10 μm Effect.That is, in order to make the polariser of below 10 μm, the method being preferably used is, at base material Applied coating solution on film and form polyvinyl alcohol resin layer, stretch each base material and manufacture polariser (there is base material film and the polarizability stacked film of the polariser on the two sides being arranged on this base material film), But, now in order to prevent curling, the two sides at base material film arranges polyvinyl alcohol resin sometimes Layer, now needs across 2 polarisers photo-curable adhesive irradiation ultraviolet radiation, therefore originally The effect of invention is particularly useful.
The thickness of polariser 5 is preferably below 10 μm, below more preferably 7 μm.Will polarization The thickness of device 5 is set as the filming of below 10 μm, beneficially polarization plates.
Polariser 5 can be to make dichromatic pigment at the polyvinyl alcohol resin through uniaxial tension Gas absorption quantity in Ceng and the polariser that obtains.As the polyethylene constituting polyvinyl alcohol resin layer Alcohol resinoid, it is possible to use polyvinyl acetate esters resin is carried out saponification and the resin that obtains. As polyvinyl acetate esters resin, except the poly-acetic acid second of the homopolymer as vinyl acetate Beyond alkene ester, it is also possible to illustrate: vinyl acetate and can be with being total to of other monomer of its copolymerization Polymers.As can enumerating such as: insatiable hunger with other monomer of vinyl acetate copolymerization With carboxylic acids, olefines, vinyl ethers, unsaturated sulfonic acid class, there is the acryloyl of ammonium Amine etc..
This polyvinyl alcohol resin is made film, and this film constitutes polariser 5.By polyvinyl alcohol The method of resin-made film forming is not particularly limited, it is possible to use known method masking, but from From the viewpoint of can be easily obtained the polariser 5 of below thickness 10 μm, preferably by polyvinyl alcohol tree The solution of fat is coated on base material film makes film.
Polariser 5 needs to be orientated by stretching, preferably with more than 5 times, the most excellent Choosing stretches with the draw ratio more than 5 times and less than 17 times.
The saponification degree of polyvinyl alcohol resin can be the scope of 80.0～100.0 moles of %, preferably It is the scope of 90.0～99.5 moles of %, the more preferably scope of 94.0～99.0 moles of %.Saponification When degree is less than 80.0 moles of %, the resistance to water of the polarization plates 1,2 obtained and humidity resistance reduce. When using the saponification degree polyvinyl alcohol resin more than 99.5 moles of %, dyeing kinetics is slack-off, raw Productivity reduces, and sometimes cannot obtain the polariser 5 with sufficient polarization property.
Saponification degree refers to the polyvinyl acetate esters resin of the raw material as polyvinyl alcohol resin Acetate (the acetoxyl group :-OCOCH comprised3) it is converted into hydroxyl by saponifying process The value that ratio represents with unit ratio (mole %), it is defined by the formula:
Saponification degree (mole %)=100 × (hydroxyl value) ÷ (hydroxyl value+acetic acid radix)
Saponification degree can be obtained according to JIS K 6726 (1994).Saponification degree is the highest, represents hydroxyl The ratio of base is the highest, therefore represents that the ratio of the acetate of suppression crystallization is the lowest.
Polyvinyl alcohol resin can be partially modified modified polyvinylalcohol.Can enumerate such as: Polyvinyl alcohol resin is utilized the alkene such as ethylene, propylene；Acrylic acid, methacrylic acid, bar The unsaturated carboxylic acids such as bean acid；The Arrcostab of unsaturated carboxylic acid, acrylamide etc. are modified and obtain Resin.Modified ratio is preferably less than 30 moles of %, and more preferably fewer than 10%.Surpass When crossing 30 moles of % modified, it is difficult to absorption dichromatic pigment, thus cannot obtain having fully The polariser 5 of polarization property.
The average degree of polymerization of polyvinyl alcohol resin is preferably 100～10000, more preferably 1500～8000, more preferably 2000～5000.The average polymerization of polyvinyl alcohol resin Degree can be tried to achieve according to JIS K 6726 (1994).
It is suitable for the example of the commercially available product of the polyvinyl alcohol resin used in the present invention, all with business The name of an article is enumerated, and comprises: " PVA124 " of Kuraray Co., Ltd. (saponification degree: 98.0～ 99.0 moles of %), " PVA117 " (saponification degree: 98.0～99.0 moles of %), " PVA624 " (saponification degree: 95.0～96.0 moles of %), " PVA617 " (saponification degree: 94.5～95.5 Mole %)；" AH-26 " of the Nippon Synthetic Chemical Industry Co., Ltd (saponification degree: 97.0～ 98.8 mole %), " AH-22 " (saponification degree: 97.5～98.5 moles of %), " NH-18 " (saponification degree: 98.0～99.0 moles of %), " N-300 " (saponification degree: 98.0～99.0 moles %)；" JC-33 " (saponification degree: 99.0 moles of VAM&POVAL Co., Ltd. of Japan More than %), " JM-33 " (saponification degree: 93.5～95.5 moles of %), " JM-26 " (soap Change degree: 95.5～97.5 moles of %), " JP-45 " (saponification degree: 86.5～89.5 moles of %), " JF-17 " (saponification degree: 98.0～99.0 moles of %), " JF-17L " (saponification degree: 98.0～ 99.0 moles of %), " JF-20 " (saponification degree: 98.0～99.0 moles of %).
The dichromatic pigment that polariser 5 is comprised (gas absorption quantity) can be iodine or dichromatic has Organic dye.The concrete example of dichroic organic dye comprises: red (Red) BR, red (Red) LR, Red (Red) R, pink (Pink) LB, magenta (Rubin) BL, purplish red (Bordeaux) GS, skyblue (Sky Blue) LG, lemon yellow (Lemon Yellow), blue (Blue) BR, indigo plant (Blue) 2R, navy blue (Navy) RY, green (Green) LG, purple (Violet) LB, purple (Violet) B, black (Black) H, black (Black) B, black (Black) GSP, Yellow (Yellow) 3G, Huang (Yellow) R, orange (Orange) LR, orange (Orange) 3R, Scarlet (Scarlet) GL, scarlet (Scarlet) KGL, Congo red, brilliant violet (Brilliant Violet) BK, sun blue (Supra Blue) G, sun blue (Supra Blue) GL, direct orange (Supra Orange) GL, direct sky blue (Direct Sky Blue), direct everbright fast orange (Direct Fast Orange) S, direct fast black (Direct Fast Black).Dichromatic pigment can be the most independent Use a kind, it is also possible to and use two or more.
(2) protecting film
Protecting film 10 can be each to comprise thermoplastic resin, such as, and chain polyolefin resin (polypropylene-based resin etc.), cyclic polyolefin hydrocarbon resins (norbornene resin etc.) etc. are poly- Olefine kind resin；The cellulose esters resinoids such as cellulose triacetate, cellulose diacetate ester； Polyethylene terephthalate, PEN, polybutylene terephthalate The polyester resins such as ester；Polycarbonate resin；(methyl) acrylic resin；Or they Mixture, the transparent resin film of copolymer etc..
The resin that cyclic polyolefin hydrocarbon resins refers to be polymerized cyclic olefin as polymerized unit total Claim, can enumerate such as: Japanese Unexamined Patent Publication 1-240517 publication, Japanese Unexamined Patent Publication 3-14882 Resin number described in publication, Japanese Unexamined Patent Publication 3-122137 publication etc..If enumerating ring-type The concrete example of polyolefin resin, then be: the open loop (co) polymer of cyclic olefin, ring-type Copolymer (the generation of the addition polymer of alkene, cyclic olefin and the chain olefin such as ethylene, propylene Table is random copolymer), and they utilize unsaturated carboxylic acid or derivatives thereof modified Graft polymers, and their hydride etc..Wherein, it is preferably used: use as ring The norborneol of the Norbornene derivatives such as the norborene of shape alkene or multi-ring Norbornene derivative Vinyl resin.
Cyclic polyolefin hydrocarbon resins is commercially available various goods.The resinoid commercially available product of cyclic polyolefin Example, all enumerate with trade name, comprise, " Topas " (Topas Advanced Polymers GmbH company system, obtains from Polyplastic Co., Ltd.), " ARTON " (JSR strain Formula commercial firm system), " ZEONOR " (Zeon Corp's system), " ZEONEX " (Zeon Corp's system), " APEL " (Mitsui Chemicals, Inc's system).
Additionally, all enumerate with trade name, it is possible to use " Escena " (hydrops chemical industry strain Formula commercial firm system), " SCA40 " (Sekisui Chemical Co., Ltd's system), " ZEONOR Film " (Zeon Corp's system) etc. make the commercially available of the cyclic polyolefin resin film of film Product are as protecting film.
Cellulose esters resinoid is the ester of cellulose and fatty acid.Cellulose esters resinoid concrete Example comprises: cellulose triacetate, cellulose diacetate ester, three cellulose propionate esters, dipropyl Acid cellulose ester.In addition it is also possible to use their copolymer or part of hydroxyl to be replaced by other The polymer that base is modified.Among those, (triacetyl is fine for particularly preferred cellulose triacetate Dimension element: TAC).Cellulose triacetate is commercially available various products, from obtaining easiness, one-tenth It is favourable for this aspect.The example of the commercially available product of cellulose triacetate, all with commodity Name is enumerated, and comprises: " Fujitac TD80 " (Fuji Photo Film Co., Ltd.'s system), " Fujitac TD80UF " (Fuji Photo Film Co., Ltd.'s system), " Fujitac TD80UZ " (Fujiphoto Co., Ltd.'s system), " Fujitac TD40UZ " (Fuji Photo Film Co., Ltd.'s system), " KC8UX2M " (Konica Minolta Opto Inc's system), " KC4UY " (Konica Minolta Opto Inc's system).
Protecting film 10 can also have the protecting film of optical function concurrently for phase retardation film, brightness enhancement film etc.. For example, it is possible to by the transparent resin film comprising above-mentioned material is stretched (uniaxial tension or twin shaft Stretching etc.), or on this film, form liquid crystal layer etc., thus make and impart arbitrary phase place The phase retardation film of difference.
Light transmittance under the wavelength 365nm of protecting film 10 is preferably smaller than 5%.Now, for ripple The protecting film of long shorter ultraviolet (light of wavelength 280nm～320nm: UV-B etc.) Absorbance is the lowest.Therefore, across photo-curable adhesive by protecting film stacking on the polarizer State under, when making adhesive solidify by irradiation ultraviolet radiation (UV-B etc.), by from Protecting film side irradiation ultraviolet radiation can not make photo-curable adhesive solidify.Therefore, the most especially need Transmittance (the fall of the light for wavelength 280nm～320nm (UV-B) of polariser to be improved Low absorbance).According to the present invention, even if the UV transmissive at such protecting film is low In the case of, owing to the transmittance for ultraviolet of polariser is high, thereby through from polariser side (opposition side of protecting film) irradiation ultraviolet radiation, can form photo-curable adhesive and fully solidify Adhesive layer.
From the viewpoint of the filming of polarization plates, the thickness of protecting film 10 be preferably 80 μm with Under, below more preferably 60 μm, more preferably below 50 μm.It addition, from guaranteeing film From the viewpoint of intensity, the thickness of protecting film 10 is usually more than 5 μm.
Hard conating, anti-dazzle can also be formed on the surface with polariser 5 opposition side of protecting film 10 The surface-treated layers (coating) such as layer, anti-reflection layer, antistatic backing, stain-proofing layer.At protecting film Surface forms the method for surface-treated layer and is not particularly limited, it is possible to use known method.
(3) adhesive layer
Adhesive layer 15 is the layer of the solidfied material comprising photo-curable adhesive.
Photo-curable adhesive refers to the glue solidified by irradiation ultraviolet radiation isoreactivity energy-ray Stick, can enumerate such as: comprise polymerizable compound and the adhesive of Photoepolymerizationinitiater initiater, The adhesive that comprises light reactive resin, comprise resin glue and the glue of photoreactivity cross-linking agent Stick etc..It should be noted that photo-curable adhesive has the advantage that 1) can be with nothing Prepared by the form of solvent type adhesive, therefore can need not drying process；2) may be used for The laminating etc. of the protecting film that moisture permeability is low, therefore compared with aqueous adhesive, the protection that can fit The kind of film is more；Deng.
As polymerizable compound, can enumerate: photo-curable epoxy compounds, photocuring The photo-curable vinyl compounds such as property acrylic compounds；Photo-curable carbamates Compound.
As Photoepolymerizationinitiater initiater, can enumerate: light cationic polymerization initiators (such as uses During photo-curable epoxy compounds), optical free radical polymerization initiator (such as use photocuring During property acrylic compounds).
The photopolymerization comprised in the gluing optical polymerism adhesive of protecting film and polariser is drawn Send out the maximum absorption wavelength of agent preferably between 280nm～320nm.At this point it is possible to use with Visible ray compares the Photoepolymerizationinitiater initiater of short wavelength side and photosensitizer etc., therefore makes display dress Postpone and be not susceptible to, by going bad that visible ray causes, therefore to provide the polarization that light resistance is excellent Plate.
(4) adhesive phase
As in figure 2 it is shown, at the outer surface (with the face of adhesive layer 15 opposition side) of polariser 5, Can be with stacking for polarization plates 1 being fitted in other component (display list of such as display device First 4) adhesive phase 2.
The binding agent forming adhesive phase 2 generally comprises with (methyl) acrylic resin, benzene Polymer based on vinyl resins, polysiloxanes resinoid etc., is added with isocyanide wherein The adhesive composition of the cross-linking agent such as ester compound, epoxide, aziridine cpd. Can also be fabricated to show light scattering adhesive phase possibly together with microgranule.
The thickness of adhesive phase 2 can be 1 μm～40 μm, is not damaging processability, durability Characteristic in the range of, preferably formed in the way of relatively thin, the most preferably 3 μm～ 25μm.The thickness of 3 μm～25 μm has good processability, and at suppression polariser 5 In change in size the most suitable.Adhesive phase 2 reduces less than cohesive during 1 μm, more than 40 μm Time be susceptible to that binding agent is prominent waits undesirable condition.
There is no particular restriction for the method for formation adhesive phase 2, can be coated with on the surface of polariser 5 Cloth comprises the adhesive composition of each composition headed by above-mentioned base polymer, and (binding agent is molten Liquid), and be dried and formed, it is also possible on partition (stripping film), it is identically formed binding agent After layer 2, this adhesive phase 2 is transferred to polariser 5.Adhesive phase 2 is formed at polariser Time on the surface of 5, can be real on the surface of the surface of polariser 5 or adhesive phase 2 as required Execute surface process, such as sided corona treatment etc..
(5) optical layers
Polarization plates 1 can also comprise other optics being layered on protecting film 10 or polariser 5 Layer.As other optical layers, can enumerate: go out and it through certain polarized light reflective display The reflective polarizing film of the polarized light of contrary character；Surface have concaveconvex shape with anti-dazzle The film of function；Surface has the film of anti-reflective function；Surface has the reflectance coating of reflection function； There is the semi-transparent semi-reflecting film of reflection function and transmission function simultaneously；Compensation film for angular field of view etc..
As the polarization corresponding to going out opposite to that character through certain polarized light reflective display The commercially available product of the reflective polarizing film of light, can enumerate such as " DBEF " (3M company system, Can obtain from Sumitomo 3M Co., Ltd. in Japan), " APF " (3M company system, in day Originally can obtain from Sumitomo 3M Co., Ltd.).
As compensation film for angular field of view, can enumerate: be coated with liquid crystal compounds also at substrate surface Through orientation, fixing optical compensation films, comprise the phase retardation film of polycarbonate resin, bag Containing the resinoid phase retardation film of cyclic polyolefin etc..
As corresponding to substrate surface be coated with liquid crystal compounds and through orientation, fix The commercially available product of optical compensation films, can enumerate: " WV film " (Fuji Photo Film Co., Ltd.'s system), " NH film " (JX Kuang stone Energy KK system), " NR film " (JX day ore deposit day Stone Energy KK system) etc..
As the commercially available product corresponding to comprising the resinoid phase retardation film of cyclic polyolefin, Ke Yilie Lift: " ARTON film " (JSR Corp.'s system), " Escena " (hydrops chemical industry Co., Ltd.'s system), " ZEONOR film " (Zeon Corp's system) etc..
<manufacture method of polarization plates>
The polarization plates of the present invention such as suitably can be manufactured by the method shown in Fig. 3.Fig. 3 institute The manufacture method of the polarization plates shown is the method for manufacturing the polarization plates 1 with protecting film, its Include following operation successively:
(1) coating coating containing polyvinyl alcohol resin at least one face of base material film Liquid, then makes it be dried, is consequently formed polyvinyl alcohol resin layer, thus obtains stacked film Resin bed formation process S10,
(2) stretch stacked film and obtain the stretching process S20 of stretched film,
(3) dichromatic pigment is utilized to carry out dyeing and shape on the polyvinyl alcohol resin layer of stretched film Become polariser, thus obtain the dyeing process S30 of polarizability stacked film,
(4) on the polariser of polarizability stacked film, in adhesive layer laminating protecting film Any one, thus obtain the bonding process S40 of laminating film,
(5) peel off removing base material film from laminating film and obtain the polarization plates of the protected film of one-side band Stripping process S50.
Hereinafter, with reference to Fig. 4～Fig. 7 while each operation is described.It should be noted that figure In identical reference marks represent same section or considerable part.
(1) resin bed formation process S10
With reference to Fig. 4, this operation be formed on the two sides of base material film 30 polyvinyl alcohol resin layer 61, 62 and obtain the operation of stacked film 100.This polyvinyl alcohol resin layer 61,62 is stretched Operation S20 and dyeing process S30 and become the layer of polariser 51,52.Polyvinyl alcohol resin Layer 61,62 can pass through the coating solution containing polyvinyl alcohol resin at base material film 30 Two sides, and make coating layer be dried and formed.Polyvinyl alcohol tree is formed by such coating The method of lipid layer, the aspect at the polariser 51,52 being readily obtained thin film is favourable.
[base material film]
Base material film 30 can be made up of thermoplastic resin, the most preferably by the transparency, mechanical strength, The thermoplastic resin that heat stability, draftability etc. are excellent is constituted.The tool of such thermoplastic resin Style comprises such as: chain polyolefin resin, cyclic polyolefin hydrocarbon resins (norborneol alkenes Resin etc.) etc. polyolefin resin；Polyester resin；(methyl) acrylic resin；Three Cellulose acetate ester, the cellulose esters resinoid such as cellulose diacetate ester；Polycarbonate resin； Polyvinyl alcohol resin；Polyvinyl acetate esters resin；Polyarylate resinoid；Polystyrene type Resin；Polyether sulfone resin；Polysulfones resin；Polyamide-based resin；Polyimide based resin； And their mixture, copolymer.
Base material film 30 can be by the one layer of resin bed comprising one kind or two or more thermoplastic resin The single layer structure constituted, it is also possible to for multilamellar being comprised one kind or two or more thermoplastic resin Resin bed stacking and the multiple structure that obtains.Base material film 30 is preferably by stretching process S20 described later Drawing of stretching polyethylene alcohols resin bed 61,62 can be suitable for during middle stretching stacked film 100 At a temperature of stretching, the resin of stretching is constituted.
As chain polyolefin resin, except the chain alkene such as polyvinyl resin, acrylic resin Beyond the homopolymer of hydrocarbon, it is also possible to enumerate: comprise the copolymer of two or more chain olefin.Bag Base material film 30 containing chain polyolefin resin at the aspect being prone to stably stretch with high multiple is Preferably.Wherein, base material film 30 more preferably comprises: polypropylene-based resin (equal as propylene The acrylic resin of polymers or the copolymer based on propylene), polythylene resin (as The polyvinyl resin of the homopolymer of ethylene or the copolymer based on ethylene).
As be suitable as constitute base material film 30 thermoplastic resin an example with propylene For the copolymer of main body be propylene with can be with the copolymer of other monomer of propylene copolymerization.
As can enumerating such as: ethylene, alpha-olefin with other monomer of propylene copolymerization. As alpha-olefin, the alpha-olefin of carbon number more than 4, more preferably carbon number are preferably used The alpha-olefin of 4～10.The concrete example of the alpha-olefin of carbon number 4～10 comprises such as: 1-butylene, The straight monoene hydro carbons such as 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-decene；3-methyl isophthalic acid- The branched monoolefins classes such as butylene, 3-Methyl-1-pentene, 4-methyl-1-pentene；Vinyl cyclohexane. Propylene with can be able to be random copolymer with the copolymer of other monomer of its copolymerization, it is also possible to For block copolymer.
The content of other monomer above-mentioned the most for example, 0.1～20 weight %, is preferably 0.5～10 weight %.The content of other monomer in copolymer can be by according to " polymer divides Analysis handbook (macromolecule analyzes Ha Application De Block ッ Network) " (nineteen ninety-five, Kinokuniya bookstore issues) The described method of page 616, carry out infrared (IR) spectroscopic assay and try to achieve.
Among above-mentioned, as polypropylene-based resin, be preferably used the homopolymer of propylene, propylene- Ethylene atactic copolymer, propylene-1-butylene random copolymer or propylene-ethylene-1-butylene random copolymerization Thing.
The stereoregularity of polypropylene-based resin the most substantially isotactic or syndiotactic.Comprise tool There is the operation of the base material film 30 of the substantially polypropylene-based resin of the stereoregularity of isotactic or syndiotactic Property relatively good, and mechanical strength in high temperature environments is excellent.
Polyester resin is the resin with ester bond, generally comprises polybasic carboxylic acid or derivatives thereof Resin with the condensation polymer of polyhydric alcohol.As polybasic carboxylic acid or derivatives thereof, it is possible to use divalent Dicarboxylic acids or derivatives thereof, can enumerate such as: p-phthalic acid, M-phthalic acid, Dimethyl terephthalate (DMT), naphthalene diformic acid dimethyl ester etc..As polyhydric alcohol, it is possible to use divalent Dihydroxylic alcohols, can enumerate such as: ethylene glycol, propylene glycol, butanediol, neopentyl glycol, ring Hexane dimethanol etc..
As the typical example of polyester resin, can enumerate: as p-phthalic acid and ethylene glycol The polyethylene terephthalate of condensation polymer.Although polyethylene terephthalate is knot Crystalline substance resin, but before crystallization processes, stretching easy to implement etc. process.As Fruit needs, then can carry out crystallization process by the heat treatment etc. when stretching or after stretching. Additionally, be also adaptable for using: by make the skeleton of polyethylene terephthalate further with its The monomer copolymerization of its kind and reduce the copolyester of crystallinity (or becoming amorphism).Make For the example of such resin, can enumerate such as: make cyclohexanedimethanol, M-phthalic acid Copolymerization and the resin etc. that obtains.The draftability of these resins is excellent, is therefore suitable for using.
If enumerating the polyester resin beyond polyethylene terephthalate and copolymer thereof Concrete example, can enumerate such as: polybutylene terephthalate (PBT), poly-naphthalenedicarboxylic acid ethylene glycol Ester, PBN, PTT, poly-naphthalenedicarboxylic acid the third two Alcohol ester, polycyclohexylene's dimethyl esters, poly-naphthalenedicarboxylic acid cyclohexanedimethyl ester, And their mixture, copolymer etc..
(methyl) acrylic resin is the compound to have (methyl) acryloyl group The resin of monomer to be constituted.The concrete example of (methyl) acrylic resin comprises such as: poly-first Poly-(methyl) acrylate such as base acrylic acid methyl ester.；Methyl methacrylate-(methyl) propylene Acid copolymer；Methyl methacrylate-(methyl) acrylate copolymer；Methyl methacrylate Ester-acrylate-(methyl) acrylic copolymer；(methyl) acrylate-styrene is common Polymers (MS resin etc.)；Methyl methacrylate and being total to of compound with alicyclic alkyl Polymers (such as, methyl methacrylate-cyclohexyl methacrylate copolymer, methacrylic acid Methyl ester-(methyl) acrylic acid norborneol ester copolymer etc.).It is preferably used with poly-(methyl) third E pioic acid methyl ester etc. poly-(methyl) acrylic acid C1-6Arrcostab is as the polymer of main component, more Be preferably used using methyl methacrylate as main component (50～100 weight %, be preferably 70～100 weight %) Tri-n-butyltin methacrylate resin.
Polycarbonate resin is to comprise gathering that monomeric unit bonding obtains via carbonate group The engineering plastics of compound, for having high-impact, thermostability, anti-flammability, the tree of the transparency Fat.The polycarbonate resin constituting base material film 30 can be: in order to reduce photoelastic coefficient The resin being referred to as modified polycarbonate that polymer backbone is modified, or improve wavelength and depend on Rely the copolymerization polycarbonate etc. of property.
Polycarbonate resin is commercially available various goods.Commercially available product as polycarbonate resin Ion, all enumerate with trade name, can enumerate: " PANLITE " (Supreme Being people is melted into strain formula Commercial firm's system), " IUPILON " (Mitsubishi engineering Plastics Co., Ltd's system), " SDPOLYCA " (Sumitomo Dow Ltd.'s system), " CALIBRE " (DOW Chemical Co., Ltd. system) etc..
Among above, from the viewpoint such as draftability, thermostability, polypropylene type tree is preferably used Fat.
For may be used for cyclic polyolefin hydrocarbon resins and the cellulose esters resinoid of base material film 30 For, quote the item that protecting film is described.Additionally, relevant to base material film 30 is above-mentioned Chain polyolefin resin, polyester resin, (methyl) acrylic resin, poly-carbonic acid Esters resin is also used as the constituent material of protecting film.
In base material film 30, in addition to above-mentioned thermoplastic resin, it is the most suitable to add Additive.As such additive, can enumerate such as: UV absorbent, antioxidation Agent, lubricant, plasticizer, releasing agent, anti-coloring agent, fire retardant, nucleator, antistatic Agent, pigment and coloring agent etc..The content of the thermoplastic resin in base material film 30 is preferably 50～100 Weight %, more preferably 50～99 weight %, more preferably 60～98 weight %, especially It is preferably 70～97 weight %.The content of the thermoplastic resin in base material film 30 is less than 50 weight During %, it is possible to the high transparent etc. that thermoplastic resin has originally cannot be shown fully.
The thickness of base material film 30 can suitably determine, typically from the workability such as intensity, operability Aspect is set out, preferably 1 μm～500 μm, more preferably 1 μm～300 μm, further preferably It is 5 μm～200 μm, most preferably 5 μm～150 μm.
[containing the coating fluid of polyvinyl alcohol resin]
Coating fluid preferably makes the powder of polyvinyl alcohol resin be dissolved in good solvent (such as water) And the polyvinyl alcohol resin solution obtained.The details of polyvinyl alcohol resin is described above.
Coating fluid can contain the additive such as plasticizer, surfactant as required.As increasing Mould agent, it is possible to use polyhydric alcohol or its condensation substance etc., can illustrate such as: glycerol, two glycerol, Triglycerin, ethylene glycol, propylene glycol, Polyethylene Glycol etc..The use level of additive is set as poly-second Resinoid 20 weight % of enol the following is applicable.
[coating of coating fluid and being dried of coating layer]
Above-mentioned coating solution suitably can be selected in the method for base material film 30 from following methods Select: bar rubbing method；The rolling methods such as reverse coating, intaglio plate coating；Mouth die coating method；Funny Number scraper for coating method；Die lip rubbing method；Spin-coating method；Silk screen rubbing method；Jetting type rubbing method； Dip coating；Spraying process etc..
When the two sided coatings coating fluid of base material film 30, it is possible to use each one side of above-mentioned method Carry out successively, it is possible to use infusion process, spraying process, other special device, at base material film 30 Two sides be coated with simultaneously.
The baking temperature of coating layer (the polyvinyl alcohol resin layer before Gan Zaoing) and root drying time Set according to the kind of the solvent included in coating fluid.Baking temperature for example, 50 DEG C～200 DEG C, preferably 60 DEG C～150 DEG C.When solvent comprises water, baking temperature is preferably more than 80 DEG C. For example, 2 minutes～20 minutes drying time.
In the diagram, formed on the two sides of base material film 30 2 polyvinyl alcohol resin layers 61, 62.When so forming polyvinyl alcohol resin layer on the two sides of base material film 30, polarization can be suppressed Property stacked film 300 (with reference to Fig. 6) the most issuable film roll bent, and can be from 1 Sheet polarizability stacked film 300 obtains 2 polarization plates, therefore in terms of the production efficiency of polarization plates It is favourable.But, it is not limited to this, it is also possible to only formed by polyvinyl alcohol resin layer On a face of base material film 30.
The thickness of the polyvinyl alcohol resin layer 61,62 in stacked film 100 be preferably 3 μm～ 30 μm, more preferably 5 μm～20 μm.As long as the polyvinyl alcohol with the thickness in the range of this Resinoid layer 61,62, through stretching process S20 described later and dyeing process S30, can obtain Dyeability to dichromatic pigment is good, polarization property is excellent and polariser below thickness 10 μm 51、52.When the thickness of polyvinyl alcohol resin layer 61,62 is more than 30 μm, polariser 51, The thickness of 52 is sometimes more than 10 μm.Additionally, the thickness of polyvinyl alcohol resin layer 61,62 During less than 3 μm, become too thin after stretching, have the tendency that dyeability is deteriorated.
Before applied coating solution, in order to improve base material film 30 and polyvinyl alcohol resin layer 61, The adhesiveness of 62, can the surface of base material film 30 implement sided corona treatment, Cement Composite Treated by Plasma, Flame (flame) process etc..
Additionally, before applied coating solution, in order to improve base material film 30 and polyvinyl alcohol resin The adhesiveness of layer 61,62, can be formed across priming coat or adhesive layer on base material film 30 Polyvinyl alcohol resin layer 61,62.
[priming coat]
Priming coat can by by priming coat formation coating solution in the surface of base material film 30, Then it is made to be dried and be formed.Priming coat formation coating fluid comprises base material film 30 and polyethylene Both alcohols resin beds 61,62 play the composition of strong adhesion to a certain degree.Priming coat is formed Resinous principle and the solvent giving such adhesion is usually contained with coating fluid.Become as resin Point, the excellent thermoplastic resins such as the transparency, heat stability, draftability is preferably used, permissible Enumerate such as: (methyl) acrylic resin, polyvinyl alcohol resin etc..Wherein, preferably Use the polyvinyl alcohol resin giving good adhesion.
As polyvinyl alcohol resin, can enumerate such as: polyvinyl alcohol resin and derivant thereof. As the derivant of polyvinyl alcohol resin, except polyvinyl formal, polyvinyl acetal Beyond Deng, can enumerate: the olefines such as polyvinyl alcohol resin ethylene, propylene are modified And the resin obtained；Carry out by unsaturated carboxylic acid classes such as acrylic acid, methacrylic acid .beta.-methylacrylic acids Modified and the resin that obtains；The resin being modified with the Arrcostab of unsaturated carboxylic acid and obtain； The resin etc. being modified with acrylamide and obtain.In above-mentioned polyvinyl alcohol resin, excellent Choosing uses polyvinyl alcohol resin.
As solvent, generally can use and can dissolve the general organic molten of above-mentioned resinous principle Agent or aqueous solvent.If enumerating the example of solvent, can enumerate such as: benzene, toluene, two Toluene etc. are aromatic hydrocarbon；The ketones such as acetone, butanone, hexone；Acetic acid second The esters such as ester, isobutyl acetate；The chlorinated hydrocarbons such as dichloromethane, trichloroethane, chloroform；Second The alcohols such as alcohol, 1-propanol, 2-propanol, n-butyl alcohol.But, the primary coat comprising organic solvent is used When layer formation forms priming coat with coating fluid, it is possible to make base material film 30 dissolve, the most same Time consider base material film 30 dissolubility select solvent.If also allowing for the impact on environment, The most preferably formed priming coat by the coating fluid using water as solvent.
In order to improve the intensity of priming coat, crosslinking can be added in priming coat formation coating fluid Agent.According to the kind of the thermoplastic resin used, cross-linking agent is from organic crosslinking agent, inorganic friendship The known cross-linking agent such as connection agent properly select suitable cross-linking agent.If enumerating cross-linking agent Example, for example, epoxies, isocyanates, twain-aldehyde compound, metal class cross-linking agent.
As epoxies cross-linking agent, it is possible to use in one pack system curing type, bi-component curing type Any one, can enumerate: Ethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, Glycerol two-or three-glycidyl ether, 1,6 hexanediol diglycidylether, trimethylolpropane tris Glycidyl ether, diglycidylaniline, diglycidyl amine etc..
As isocyanates cross-linking agent, can enumerate: toluene di-isocyanate(TDI), hydrogenated toluene Diisocyanate, trimethylolpropane-toluene di-isocyanate(TDI) addition product, triphenyl methane three are different Cyanate, di-2-ethylhexylphosphine oxide (4-phenylmethane) triisocyanate, isophorone diisocyanate, And their ketoxime blocks thing or phenol end-blocking thing etc..
As twain-aldehyde compound cross-linking agent, can enumerate: Biformyl, malonaldehyde, butanedial, penta 2 Aldehyde, malealdehyde, o-phthalaldehyde(OPA) etc..
As metal class cross-linking agent, can enumerate such as: slaine, metal-oxide, metal Hydroxide, organo-metallic compound.As slaine, metal-oxide, metallic hydrogen oxidation Thing, can enumerate such as: magnesium, calcium, aluminum, ferrum, nickel, zirconium, titanium, silicon, boron, zinc, copper, Vanadium, chromium, stannum etc. have the salt of metal, oxide and the hydroxide of the atomicity of more than bivalence Thing.
Organo-metallic compound refers to have at least 1 direct key on metallic atom in intramolecular Close and have organic group or be bonded with the change of structure of organic group across oxygen atom or nitrogen-atoms etc. Compound.Organic group refers to the monovalence including at least carbon or the group of multivalence, the most permissible For alkyl, alkoxyl, acyl group etc..Additionally, bonding not only refers to covalent bond, it is also possible to for such as The such coordinate bond formed by coordination of chelate compound.
The example being suitable for of organo-metallic compound comprises: organic titanic compound, organic zirconium chemical combination Thing, organo-aluminum compound, organo-silicon compound.Organo-metallic compound can the most only use 1 Kind, it is also possible to and use two or more.
As organic titanic compound, can enumerate such as: tetra-n-butyl titanate, metatitanic acid four isopropyl The titanium ortho acid such as ester, butyltitanate dimer, metatitanic acid four (2-ethylhexyl) ester, metatitanic acid four methyl ester Esters；Titanium acetylacetone, four titanium acetylacetones, poly（titanium acetylacetonate）, octylene glycolic titanium, The titanium chelate classes such as lactic acid titanium, triethanolamine titanium, ethylacetoacetate titanium；Multi-hydroxy stearic acid The acylated titanium class such as titanium etc..
As organic zirconate, can enumerate such as: n Propanoic acid zirconium, n-butyric acie zirconium, tetrem Acyl acetone zirconium, single acetyl acetone zirconium, bis-acetylacetonate zirconium, acetylacetone,2,4-pentanedione-diacetyl acetate ethyl ester Zirconium etc..
As organo-aluminum compound, can enumerate such as: aluminium acetylacetonate, aluminum organic acid chelate Thing etc..As organo-silicon compound, can enumerate such as: previously at organic titanic compound with have The compound that the part illustrated in machine zirconium compounds is bonded with silicon.
In addition to above low molecule type cross-linking agent, it is also possible to use methylolated melamine The polymer electrolyte cross-linking agent such as resin, Polyamide Epoxy.If enumerating Polyamide Epoxy The example of commercially available product, can enumerate: sold by Taoka Chemical Industries Co. Ltd. " SUMIREZ RESIN650 (30) " or " SUMIREZ RESIN675 " (are business The name of an article) etc..
When use polyvinyl alcohol resin is as the resinous principle of formation priming coat, it is preferably used Polyamide Epoxy, methylolated melamine resin, twain-aldehyde compound cross-linking agent, metal-chelating Compounds cross-linking agent etc. are as cross-linking agent.
The ratio of the resinous principle in priming coat formation coating fluid and cross-linking agent is from relative to resin Composition 100 parts by weight of crosslinking agent is about in the scope of 0.1～about 100 weight portions, becomes according to resin Kind, the kind etc. of cross-linking agent divided suitably determine, particularly preferably from about 0.1～about 50 The scope of weight portion selects.Make it solid it addition, priming coat formation coating fluid preferably sets Shape substrate concentration is about 1～about 25 weight %.
The thickness of priming coat is preferably from about 0.05 μm～about 1 μm, more preferably 0.1 μm～ 0.4μm.Time thinner than 0.05 μm, improve base material film 30 and polyvinyl alcohol resin layer 61,62 The effect of adhesion little, during than 1 μ m-thick, be unfavorable for the filming of polarization plates.
Can be with polyvinyl alcohol in the method for base material film 30 by priming coat formation coating solution The coating fluid that resinoid layer is formed is identical.Priming coat is coated on wants pva coating resinoid On the face (one or two sides of base material film 30) of the coating fluid that layer is formed.Comprise priming coat shape The baking temperature of the coating layer of one-tenth coating fluid and drying time are according to the solvent contained by coating fluid Kind and set.Baking temperature for example, 50 DEG C～200 DEG C, preferably 60 DEG C～150 DEG C.Molten When agent comprises water, baking temperature is preferably more than 80 DEG C.For example, 30 seconds～20 drying time Minute.
When arranging priming coat, there is no particular restriction for the coating squence on base material film 30, such as may be used With after the two sides of base material film 30 forms priming coat, form polyvinyl alcohol resin layer on two sides, Can also after the one side of base material film 30 sequentially forms priming coat and polyvinyl alcohol resin layer, The another side of base material film 30 sequentially forms priming coat and polyvinyl alcohol resin layer.
(2) stretching process S20
With reference to Fig. 5, this operation will be for will comprise base material film 30 and polyvinyl alcohol resin layer 61,62 Stacked film 100 stretch, thus obtain comprising stretched base material film 30 ' and polyvinyl alcohol The operation of the stretched film 200 of resin bed 61,62.Stretch processing is usually uniaxial tension.
The draw ratio of stacked film 100 suitably can select according to desired polarization characteristic, excellent Phase selection for the raw footage of stacked film 100 for more than 5 times and less than 17 times, more preferably more than 5 times and less than 8 times.When draw ratio is less than 5 times, polyvinyl alcohol resin layer 61,62 It is orientated the most fully, therefore cannot improve the degree of polarization of polariser 51,52 fully.The opposing party Face, when draw ratio is more than 17 times, easily produces rupturing of film, and stretched film when stretching The thickness of 200 becomes too thin, it is possible in subsequent handling, processability and operability reduce.
Stretch processing is not limited to one section of stretching, it is also possible to multistage is carried out.Now, the stretching of multistage Process and all can carry out continuously before dyeing process S30, it is possible to so that second segment is later Stretch processing is carried out with the dyeing process in dyeing process S30 and/or crosslinking Treatment simultaneously.Thus When carrying out stretch processing with multistage, preferably reach more than 5 with whole stage summations of stretch processing The mode of draw ratio again carries out stretch processing.
Stretch processing is except can be that the longitudinal direction stretched along film length direction (film carriage direction) is drawn Beyond stretching, it is also possible to for the cross directional stretch stretched along film width or oblique extension etc..As Longitudinal stretching mode, can enumerate: use roller carry out stretching between the roller stretched, compression stretching, Use the stretching etc. of chuck (clip), as cross directional stretch mode, can enumerate: tentering method Deng.Stretch processing can use any one in wet tensile method, dry-stretch process, but It is that to use dry-stretch process be preferred for can leniently selecting in terms of draft temperature in scope 's.
Draft temperature is set as being shown to stretching polyethylene alcohols resin bed 61,62 and base material More than the temperature of the mobility of the degree of film 30 entirety, the preferably phase transition temperature of base material film 30 The scope of-30 DEG C to+30 DEG C of (fusing point or glass transition temperature), more preferably-30 DEG C extremely The scope of+5 DEG C, the more preferably scope of-25 DEG C to+0 DEG C.Base material film 30 comprises multiple During resin bed, above-mentioned phase transition temperature refers in the phase transition temperature that the plurality of resin bed shows the highest Phase transition temperature.
When draft temperature is lower than phase transition temperature-30 DEG C, it is difficult to achieve over the high multiple stretching of 5 times, Or the mobility of base material film 30 is too low and has the tendency that is difficult to stretch processing.Draft temperature When exceeding phase transition temperature+30 DEG C, the mobility of base material film 30 is excessive and has the tendency that is difficult to stretch. Draft temperature within the above range, more preferably more than 120 DEG C because easily achieving over The high draw ratio of 5 times.This is because, when draft temperature is more than 120 DEG C, even if for exceeding The high draw ratio of 5 times, also without difficulty in stretch processing.
As the heating means of the stacked film 100 in stretch processing, have: region heating (example As, be blown into hot blast and regulate to the such stretch zones of heating furnace of set point of temperature heating Method)；It is the method that roller itself is heated when using roller stretching；Heater heating (by infrared heater, halogen heater, baffle heater etc. is arranged on stacked film 100 Up and down, the method that radiant heat carries out heating is utilized) etc..Between roller in stretching mode, from stretching From the viewpoint of the uniformity of temperature, favored area heating.Now 2 nip rolls are to setting Put in the stretch zones after homoiothermic, it is possible to be arranged on outside stretch zones, but in order to prevent layer Folded film 100 and the bonding of nip rolls, be preferably provided at outside stretch zones.
It should be noted that in the case of the heating of region, (example in draft temperature refers to region In heating furnace) ambient temperature, in the case of heater heating, draft temperature refers to Ambient temperature in stove when heating in stove.Additionally, in the side that roller itself is heated In the case of method, draft temperature refers to the surface temperature of roller.
Before stretching process S20, can arrange at the preheating that stacked film 100 is preheated Science and engineering sequence.As pre-heating mean, it is possible to use the side identical with the heating means in stretch processing Method.Stretch processing mode is between roller in the case of stretching, and preheating can be by the folder of upstream side Before roller, pass through in, by after any instant carry out.Stretch processing mode is hot-rolling stretching In the case of, preheating is preferably carrying out by the moment before hot-rolling.Stretch processing mode is for using In the case of chuck stretching, preheating is preferably carried out from the front moment at expansion jaw separation.Preheating Temperature is preferably the scope of-50 DEG C to ± 0 DEG C of draft temperature, more preferably-the 40 of draft temperature DEG C to the scope of-10 DEG C.
Additionally, heat setting treatment process can be arranged after the stretch processing of stretching process S20. It is while being protected when utilizing clip to clamp the end of stretched film 200 that heat setting processes Hold tension while in the process of crystallized temperature heat treatment carried out above.By this heat setting Process, promote the crystallization of polyvinyl alcohol resin layer 61 ', 62 '.The temperature that heat setting processes is excellent Elect-0 DEG C of draft temperature～-0 DEG C of the scope of-80 DEG C, more preferably draft temperature～-50 DEG C as Scope.
(3) dyeing process S30
With reference to Fig. 6, this operation is by the polyvinyl alcohol resin layer 61 ', 62 ' of stretched film 200 Carry out dyeing and make its gas absorption quantity to make the operation of polariser 51,52 with dichromatic pigment. Through this operation, can obtain being laminated with the inclined of polariser 51,52 on the two sides of base material film 30 ' Shaking property stacked film 300.
Dyeing process can be by by molten containing dichromatic pigment of stretched film 200 mass-impregnation Liquid (staining solution) is carried out.As staining solution, it is possible to use by above-mentioned dichromatic color The solution that element is dissolved in solvent and obtains.As the solvent of staining solution, generally use water, also Organic solvent having a miscibility with water can be added further.Dichromatic color in staining solution The concentration of element is preferably 0.01～10 weight %, and more preferably 0.02～7 weight % are the most excellent Elect 0.025～5 weight % as.
When using iodine as dichromatic pigment, in the staining solution containing iodine, preferably it is also added with iodine Compound, because staining efficiency can be improved further.As iodide, can enumerate such as: Potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, iodate Asia lead, Hydro-Giene (Water Science)., Barium iodide, calcium iodide, Tin diiodide., titanium iodide etc..The concentration of the iodide in staining solution It is preferably 0.01～20 weight %.Among iodide, preferably add potassium iodide.Add potassium iodide Time, the ratio of iodine and potassium iodide is preferably the scope of 1:5～1:100 with mass ratio range, more excellent Elect the scope of 1:6～1:80, the more preferably scope of 1:7～1:70 as.
The stretched film 200 dip time in staining solution is usually 15 seconds～the model of 15 minutes Enclose, preferably 30 seconds～3 minutes.Additionally, the temperature of staining solution is preferably 10 DEG C～60 DEG C Scope, more preferably 20 DEG C～the scope of 40 DEG C.
It should be noted that dyeing process S30 can be carried out before stretching process S20, it is possible to To carry out with these operations simultaneously, but in order to make to be adsorbed in two colors of polyvinyl alcohol resin layer Property pigment can be orientated well, preferably stacked film 100 is being implemented drawing the most to a certain degree Dyeing process S30 is implemented after stretching process.That is, except implementing to draw by utilizing stretching process S20 Stretch process until the stretched film 200 that reaches target multiple and obtain supply to dyeing process S30 with Outward, it is also possible to utilize stretching process S20 to carry out stretch processing with the multiple less than target, then Stretch processing is implemented until total draw ratio reaches target multiple in dyeing process S30.As The embodiment of the latter, can enumerate: 1) in stretching process S20, with less than target multiple Carry out stretch processing, then in the dyeing process of dyeing process S30, carry out stretch processing and make Total draw ratio reaches the mode of target multiple；Or as described later, carry out after processing in dyeing During crosslinking Treatment, 2) carry out at stretching with the multiple less than target in above-mentioned stretching process S20 Reason, then the dyeing at dyeing process S30 carries out stretch processing until total draw ratio in processing Less than the degree of target multiple, in crosslinking Treatment, then carry out stretch processing make final total Draw ratio reach target multiple mode etc..
Dyeing process S30 can comprise the crosslinking Treatment operation implemented after then dyeing processes.Hand over Connection processes can be by comprising the solution (crosslinker solution) of cross-linking agent through hyperchromatic film immersion In and carry out.As cross-linking agent, it is possible to use known material, can enumerate such as: The boron compound such as boric acid, Borax, Biformyl, glutaraldehyde etc..Cross-linking agent can only be used alone 1 Kind, it is also possible to and use two or more.
Specifically, crosslinker solution can be that cross-linking agent is dissolved the solution obtained in a solvent. As solvent, such as, can use water, but can also comprise having a miscibility with water organic Solvent.The concentration of the cross-linking agent in crosslinker solution is preferably the scope of 1～20 weight %, more preferably It it is the scope of 6～15 weight %.
Crosslinker solution can comprise iodide.By the interpolation of iodide, can make polariser 51, Polarization property in the face of 52 is evenly.As iodide, can enumerate such as: potassium iodide, Lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, Copper diiodide, barium iodide, iodate Calcium, Tin tetraiodide., titanium iodide etc..The concentration of the iodide in crosslinker solution is preferably 0.05～15 Weight %, more preferably 0.5～8 weight %.
It is usually 15 seconds～20 minutes through hyperchromatic film dip time in crosslinker solution, It is preferably 30 seconds～15 minutes.It addition, the temperature of crosslinker solution is preferably 10 DEG C～90 DEG C Scope.
It should be noted that crosslinking Treatment can be by coordinating cross-linking agent in staining solution Process with dyeing and carry out simultaneously.In addition it is also possible to carry out stretch processing in crosslinking Treatment.? The concrete mode implementing stretch processing in crosslinking Treatment is described above.In addition it is also possible to use group The crosslinker solution of more than two kinds becoming different carries out the place that impregnated in crosslinker solution of more than 2 times Reason.
Preferably it is carried out after dyeing process S30 and before bonding process S40 described later Operation and drying process.Matting generally comprises water matting.Water cleaning treatment can be led to Cross the film immersion after dyeing being processed or after crosslinking Treatment at the pure water such as ion exchange water, distilled water In carry out.Water cleaning temperature is usually 3 DEG C～50 DEG C, preferably 4 DEG C～the scope of 20 DEG C.? Dip time in water is usually 2 seconds～300 seconds, preferably 3 seconds～240 seconds.
Matting can be the group of water matting and the matting utilizing iodide solution Close.Additionally, water matting and/or the cleaning that uses in utilizing the cleaning treatment of iodide solution In liquid, in addition to water, it is also possible to suitably contain methanol, ethanol, isopropanol, butanol, third The liquid alcohols such as alcohol.
As the drying process carried out after matting, natural drying can be used, ventilate and do The most suitable methods such as dry, heat drying.Such as during heat drying, baking temperature is usually 20 DEG C～95 DEG C, it is typically about 1 minute～about 15 minutes drying time.
(4) bonding process S40
With reference to Fig. 7, this operation is on the polariser 51 of polarizability stacked film 300, i.e. partially Shake on the face with opposition side, base material film 30 ' side of device 51, across adhesive layer laminating protecting film 10 And obtain the operation of laminating film 400.
Protecting film 10 is fitted on polariser 51 across adhesive layer 15.Across adhesive layer The laminating of protecting film can be enumerated such as: uses known means that adhesive is coated on protecting film 10 and/or the binding face of polariser 51, across this adhesive coating layer by protecting film 10 with partially The device 51 that shakes is overlapping, and uses the method that doubling roller etc. carries out fitting.
When using photo-curable adhesive as adhesive, after stating laminating on the implementation, lead to Cross the curing process irradiating active energy beam and make photo-curable adhesive solidify.Active-energy The kind of ray is not particularly limited, and is preferably and has peak wavelength at below wavelength 400nm Active energy beam (ultraviolet), more preferably has between wavelength 280nm～320nm The UV-B of peak wavelength.
As the light source of active energy beam, be not particularly limited, be preferably used high voltage mercury lamp, Low pressure mercury lamp, medium pressure mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, black light lamp, microwave excitation mercury lamp, Metal halide lamp etc..
Can be according to the composition of photo-curable adhesive to the intensity of illumination of photo-curable adhesive Suitably determine, preferably set and make polymerization initiator is activated the irradiation of effective wavelength region Intensity is 0.1～6000mW/cm2.Exposure rate is 0.1mW/cm2Time above, the response time Will not become long, exposure rate is 6000mW/cm2Time following, occur because of from radiation of light source The solidification of light and heat curable adhesive time the xanthochromia of photo-curable adhesive that caused of heating Or the probability of the deterioration of polariser 51,52 is little.
About the light irradiation time to photo-curable adhesive, it is also possible to gluing according to photo-curable The composition of agent and suitably determine, preferably set make with above-mentioned exposure rate and irradiation time long-pending The integration light quantity represented is 10～10000mJ/cm2.Integration light quantity is 10mJ/cm2Time above, Can produce and enough make curing reaction enter more reliably from the active matter of polymerization initiator OK, integration light quantity is 10000mJ/cm2Time following, irradiation time will not become long, Ke Yibao Hold good productivity ratio.
On polariser 51 during laminating protecting film 10, in polariser 51 side of protecting film 10 Surface, in order to improve and the adhesivity of polariser 51, can carry out Cement Composite Treated by Plasma, corona The surfaces such as process, ultraviolet treatment with irradiation, flame (flame) process, saponification process process (easily Gluing process), wherein, preferably carry out Cement Composite Treated by Plasma, sided corona treatment or saponification and process. Such as when protecting film comprises cyclic polyolefin hydrocarbon resins, generally carry out Cement Composite Treated by Plasma or corona Process.During additionally, comprise cellulose esters resinoid, typically carry out saponification process.As saponification Process, can enumerate: be immersed in the method in the aqueous alkali such as sodium hydroxide or potassium hydroxide.
(5) stripping process S50
This operation is to peel off to remove base material from the laminating film 400 obtained by laminating protecting film The operation of film 30 ' (with polariser 52).Via this operation, can obtain at polariser 51 One side is laminated with the polarization plates 1 of the protected film of one-side band of protecting film 10.
There is no particular limitation for the method for stripping removing base material film 30 ', it is possible to use with common band The method having the stripping process of the partition (stripping film) carried out in the polarization plates of binding agent identical is entered Row is peeled off.Base material film 30 ' can be peeled off after bonding process S40 immediately, it is also possible in laminating After operation S40, temporarily it is wound into a roll in tubular, then operation later and unreels Peel off.
<manufacturing the preferred implementation of the polariser of the present invention>
There is no particular restriction to realize the method for the absorbance of the polariser of regulation in the present invention, such as, The control of regulation of potassium iodide content in the dyeing liquor used in dyeing process is utilized by enforcement Make and/or utilize the boric acid content in the crosslinker solution used in cross-linking process step and potassium iodide content The control of regulation, the absorbance of polariser can be efficiently controlled.It addition, pass through dyer Stopping in the temperature of cleanout fluid of use, cleanout fluid in the matting after cross-linking process step in sequence Stay the time, it is also possible to effectively control the absorbance of polariser.
Potassium iodide content in dyeing liquor is different, relative to solvent according to the implementation of dyeing During (water etc.) 100 weight portion, the amount of potassium iodide is preferably below 10 weight portions, more preferably Below 7 weight portions, more preferably below 5 weight portions.By reducing the iodate in dyeing liquor The content of potassium, easily controls the absorbance of polariser within the scope of the invention.
It addition, implement crosslinking by the way of utilizing 2 kinds of crosslinkings groove (crosslinker solution) with two sections Operation, and regulate the boric acid content in the crosslinker solution of the second groove and the ratio of potassium iodide content, Effectively the absorbance of polariser can be controlled within the scope of the invention.Specifically, exist In the crosslinker solution of the second groove, relative to solvent (water etc.) 100 weight portion, boric acid content is preferred Being 5.0～10.0 weight portions, potassium iodide content is preferably below 10 weight portions, and more preferably 7 Below weight portion, more preferably below 5 weight portions.It should be noted that boric acid content And there is dependency relation between potassium iodide content, when boric acid is more, potassium iodide is less, the most permissible Efficiently control the absorbance of polariser.Otherwise, when boric acid is less, by increasing potassium iodide Number, also have and the absorbance of polariser can be controlled tendency within the scope of the invention.
If the temperature of the cleanout fluid used in matting is higher, then easily by the suction of polariser Luminosity control within the scope of the invention, therefore it is preferably more than 5 DEG C, more preferably 7 DEG C with On.But, when excessively improving the temperature of cleanout fluid, the tone having Nicol crossed is bright The undesirable condition of xanthochromia is there is when aobvious change indigo plant or heat resistant test.It is therefore preferable that use rinse bath and Two segmented modes cleaning spray thrower are carried out operation, are set by the rinse liquid temperature in rinse bath For relatively low temperature, and higher temperature will be set as from the rinse liquid temperature cleaning spray thrower ejection Degree.Now, preferably the rinse liquid temperature in rinse bath is set as 5 DEG C～13 DEG C, will be from cleaning The rinse liquid temperature of spray thrower ejection is set as 13 DEG C～20 DEG C.It addition, the time of matting Total be preferably from about 5 seconds～about 60 seconds.
But, the factor of the absorbance generation impact of polariser be there is also some other factorses, Owing to these factors make absorbance change, meet above-mentioned condition so not being only.As Such factor, can enumerate such as: draw ratio, stretching contracting width, draft temperature etc..
Specifically, when draw ratio is too high, it is difficult to control absorbance, the most final total Draw ratio is preferably less than 6.0 times.On the other hand, when multiple is too low, it is impossible to carry out well Complex is formed, and the most final total draw ratio is preferably more than 5.0 times.It addition, stretching When temperature is too high, it is difficult to control to the extinction of polariser due to the carrying out of crystallization of polyvinyl alcohol Degree, thus draft temperature is preferably less than 170 DEG C.
It should be noted that it is recited herein in the range of an example.Permissible by combinations thereof Determine final absorbance, even if therefore the manufacturing condition of part is beyond above-mentioned scope, it is also possible to Find out the manufacturing condition of the absorbance realizing the present invention, can also be obtained this in this case Bright target effect.
<display device>
The polarization plates of the present invention can apply to display device.With reference to Fig. 2, this display device can The polarization plates of the invention described above to comprise display unit 4 and be arranged on its at least one face 1。
Polarization plates 1 can use the adhesive phase 2 of the outer surface being arranged on polariser 5 and configure, It is fitted on display unit 4.In such display device, the protecting film 10 of polarization plates 1 Form the outer surface (typically outmost surface) of display device.
The typical example of display device is to show the liquid crystal indicator with unit 4 is liquid crystal cells, But can also be other display devices such as organic el device.In a display device, polarization plates is joined Put at least one face at display unit 4 but it also may be arranged in two sides.
When display device is liquid crystal indicator, generally polarization plates is arranged in the two of liquid crystal cells Face.In such a case, it is possible to the polarization plates on two sides is the polarization plates of the present invention, it is also possible to only The polarization plates of side is the polarization plates of the present invention.In the latter, the polarization plates of the present invention can be The polarization plates of the front side (visible side) on the basis of liquid crystal cells, it is also possible to for rear side (backlight Side) polarization plates.As liquid crystal cells, it is possible to use the liquid crystal cells of the most known type.
Embodiment
Below, it is shown that embodiment and comparative example are to further illustrate the present invention, but the present invention Do not limited by these examples.
<embodiment 1>
(1) priming coat formation process
By pva powder, (" Z-200 " of the Nippon Synthetic Chemical Industry Co., Ltd puts down The all degree of polymerization 1100,99.5 moles of % of saponification degree) it is dissolved in the hot water of 95 DEG C, thus prepare The polyvinyl alcohol water solution of concentration 3 weight %.By cross-linking agent (Tian Ganghua in the aqueous solution obtained Learn " the SUMIREZ RESIN650 " of Industrial Co., Ltd) with relative to polyvinyl alcohol powder End 6 weight portions are that the ratio of 5 weight portions mixes, thus obtain priming coat formation coating Liquid.
Then, un-stretched polypropylene (PP) film preparing thickness 90 μm as base material film is (molten Point: 163 DEG C), sided corona treatment is implemented on the two sides of base material film.Then, minor diameter notch board is used Coating machine, by the above-mentioned priming coat formation coating solution sided corona treatment in the side of base material film On face, and it is dried 10 minutes at 80 DEG C, thus forms the priming coat of thickness 0.2 μm.Then, The face of the opposition side of base material film is also formed identical priming coat.
(2) making (resin bed formation process) of stacked film
By pva powder (" PVA124 " of Kuraray Co., Ltd., average degree of polymerization 2400, saponification degree 98.0～99.0 moles of %) it is dissolved in the hot water of 95 DEG C, thus prepare dense Spend the polyvinyl alcohol water solution of 8 weight %, and be coated with as polyvinyl alcohol resin layer formation Cloth liquid.
Use die lip coating machine, above-mentioned polyvinyl alcohol resin layer formation coating solution is existed Above-mentioned (1) is formed at the base coating surface on the two sides of base material film, is then dried at 80 DEG C 20 minutes, on priming coat, thus form polyvinyl alcohol resin layer, thus obtain comprising poly-second The stacked film of enol resinoid layer/priming coat/base material film/priming coat/polyvinyl alcohol resin layer.
(3) making (stretching process) of stretched film
For the stacked film made in above-mentioned (2), floating type longitudinal uniaxial stretching device is used to exist 160 DEG C of free end uniaxial tensions implementing 5.8 times, thus obtain stretched film.Poly-second after stretching The thickness of enol resinoid layer amounts to 6.1 μm.
(4) making (dyeing process) of polarizability stacked film
By the stretched film made in above-mentioned (3) at the dyeing water comprising iodine and 30 DEG C of potassium iodide Dipping in solution (every 100 weight parts waters comprise iodine 0.6 weight portion, potassium iodide 10 weight portion) About 180 seconds, thus the dyeing carrying out polyvinyl alcohol resin layer processes, then pure with 10 DEG C Water-wash away unnecessary dyeing aqueous solution.
Then, at first crosslinking aqueous solution (every 100 weight parts water bags of borated 78 DEG C of bag Boronic acid containing 9.5 weight portion) in dipping 120 seconds, then, comprising the 70 of boric acid and potassium iodide DEG C second crosslinking aqueous solution (every 100 weight parts waters comprise boric acid 9.5 weight portion, potassium iodide 4 Weight portion) in dipping 60 seconds, thus carry out crosslinking Treatment.Then, clean with the pure water of 10 DEG C 10 seconds, be finally dried 300 seconds at 40 DEG C, thus obtain comprising polariser/priming coat/base material film/ The polarizability stacked film of priming coat/polariser.The thickness of polariser amounts to 6.7 μm.
(5) making (bonding process and stripping process) of polarization plates
Prepare cyclic polyolefin resin film (" ZD12 " of Zeon Corp, thickness Spend 50 μm), as being arranged in outside (visible side) when polarization plates being arranged on display unit Protecting film.Light transmittance under the wavelength 365nm of this protecting film is 2.6%.It should be noted that Measuring of light transmittance uses the spectrophotometer (UV2450) of Shimadzu Scisakusho Ltd in fact Execute.
After the binding face enforcement sided corona treatment to this protecting film, minor diameter notch board is utilized to be coated with Machine be coated with on this sided corona treatment face photo-curable adhesive (Asahi Denka Co., Ltd. " KR-70T "), across the coating layer of this adhesive, protecting film is configured system in above-mentioned (4) On the polariser of the side of the polarizability stacked film made, doubling roller is then used to fit.
Then, high voltage mercury lamp is used, by the polariser side with protecting film opposition side, with UVB's Integration light quantity is 250mJ/cm2Mode, photo-curable adhesive irradiation ultraviolet radiation (that is, is made Adhesive layer is irradiated by ultraviolet by 2 polarisers), thus make adhesive solidify And form adhesive layer, thus obtain comprising protecting film/adhesive layer/polariser/priming coat/base material The laminating film (bonding process) that the layer of film/priming coat/polariser is constituted.
Then, removing base material film/priming coat/polariser is peeled off (with protecting film from the laminating film obtained The polariser of opposition side) layer constitute (stripping process).This layer comprising base material film constitutes appearance It is easily peeled, has obtained the one-side band of the layer composition comprising protecting film/adhesive layer/polariser/priming coat The polarization plates of protected film.
<embodiment 2～6, comparative example 1～4>
Except the amount of the boric acid that will comprise in the 2nd crosslinking aqueous solution and potassium iodide is (relative to every 100 The number of weight parts water) and the temperature of rinsing bowl and washing spray thrower be set as such as institute in table 1 Beyond showing, in the way of similarly to Example 1, polarizability stacked film and polarization plates are made.
[absorbance measurement of polariser]
By by embodiment 1～6 and the polarizability stacked film that obtains of comparative example 1～4 (do not fit guarantor Cuticula) unilateral polariser peel off from base material film, for remaining in the polariser on base material film (that is, comprising the sample film that the layer of " base material film/priming coat/polariser " is constituted), measure extinction Degree.Absorbance uses absorptiometer (Japan Spectroscopy Corporation's system: V7100) to be measured, and enters Mensuration under each wavelength of row wavelength 280nm to wavelength 320nm.As V7100, use can To measure the type (window material type as quartz glass) of ultraviolet region.At wavelength 280nm In mensuration to each wavelength of wavelength 320nm, V7100 is provided as polarized light and separates The Glan thomson prism of element, obtains sample film to become relative to this Glan thomson prism Absorbance when configuring for the mode of Nicol crossed position and by the sample of this state The meansigma methods of absorbance during the configuration of film 90-degree rotation, using this meansigma methods as the absorbance of sample.
Then, following formula is used to calculate the absorbance under each wavelength.
Absorbance=-log under each wavelength10(absorbance (%)/100 under each wavelength)
Then, the maximum in the absorbance in the range of wavelength 280nm to wavelength 320nm is used It is worth the maximum absorbance as this sample.The maximum absorbance of each sample film is shown in table 1.
[test of gridiron pattern tack]
By by embodiment 1～6 and the polarization plates that obtains of comparative example 1～4 with protecting film opposition side Face use pressure-sensitive adhesive (LINTEC Co., Ltd. system: P-3132) fit on a glass, Cutter are used protecting film only to carry out chessboard trellis cutting from protecting film side, to form 100 The grid that 1mm is square, is carried out according to " JIS D0202 4.15 gridiron pattern tack test method " Orthogonal cutting test.Will be unstripped and that remain grid number is shown in table 1 after test.
[hot resistance test]
In order to assess the monomer reaction rate of the photo-curable adhesive in adhesive layer, carry out moisture-proof Heat test.When remaining unreacted monomer in adhesive layer, can be occurred by hot resistance test The decolouring of polariser.Use binding agent (LINTEC Co., Ltd. system: P-3132) will be by implementing Example 1～6 and the face with protecting film opposition side of polarization plates that obtains of comparative example 1～4 be fitted in nothing On alkali glass plate, then place 48 hours in the environment of temperature 80 DEG C, humidity 90%RH.
Then, the same polarization plates of hot resistance test will be not carried out to become crossed Nicol rib The mode of the relation of mirror is fitted on the face contrary with the polarization plates after test of alkali-free glass, and It is observed in backlight by darkroom.For there is the polarization plates of decolouring, decolouring is to nothing Color is transparent and complete light leak.Conversely, for do not occur decolouring polarization plates, for original state Completely black.Observed result is shown in table 1.
Table 1
Reference
1 polarization plates
10 protecting film
15 adhesive layers
2 adhesive phases
30 base material films
30 ' stretched base material films
4 display unit
5,51,52 polariser
61,62 polyvinyl alcohol resin layer
The polyvinyl alcohol resin layer of 61 ', 62 ' drawns
100 stacked films
200 stretched film
300 polarizability stacked films
400 laminating films

Claims (6)

1. a polariser, the maximum absorbance under its wavelength 280nm～320nm be 0.70 with Under.
2. a polarization plates, it has: the polariser described in claim 1, and across comprising The adhesive layer of the solidfied material of photopermeability adhesive is layered in the protecting film on described polariser.
3. polarization plates as claimed in claim 2, wherein, the wavelength 365nm of described protecting film Under light transmittance less than 5%.
4. polarization plates as claimed in claim 2 or claim 3, wherein, described photo-curable adhesive Containing maximum absorption wavelength Photoepolymerizationinitiater initiater between 280nm～320nm.
5. the polarization plates as according to any one of claim 2～4, wherein, described polariser Thickness be below 10 μm.
6. a polarizability stacked film, it has: base material film, and is arranged on the two of this base material film Polariser described in the claim 1 in face.
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